Process for making ozonides by reacting ozone with superoxide



United States Patent 3,139,327 PROCESS FOR MAKING OZONIDES BY REACTING OZONE WITH SUPEROXIDE Mervin D. Marshall, Fombell, and Raymond F. Bratton,

Evans City, Pa., assignors to Gallery Chemical Company, Pittsburgh, Pa., a corporation of Pennsylvania No Drawing. Filed Mar. 7, 1960, Ser. No. 13,383

14 Claims. (Cl. 23-184) This invention relates to a new method for the production of ozonides.

Ozonides, as referred to throughout this specification, are compounds having the O anion. Such compounds have in the past at times been referred to as ozonates, but presently approved nomenclature names these compounds as ozonides.

Heretofore, no good way to make ozonides has been known. Certain methods which were used have invariably resulted in very low yields and involve difficult recovery and purification techniques. These methods also were specific in their nature and were'not applicable to any wide variety of ozonides. Because of the relative insta bility of these compounds, these tedious processes have not been satisfactory because the products which are obtained tend to decompose during the processing steps required.

It is an object of this invention to provide a new method of making ozonides which is applicable to the production of several such compounds, including ozonides of alkalimetals, alkaline earth metals and quaternary ammonium cations.

Another object is to provide a method ofrmaking ozonides in which higher yields are obtained and less complicated procedures are required than in the prior known methods.

Still other objects-will become apparent from time hereinafter. The basisfor this invention is our discovery that ozone time to will react with certain superoxides to produce the corre-- sponding ozonide iii-yields much better than could be obtained by any' other method. The process does-snot require special conditions and recovery is effected in a relatively simple and straightforward manner. Using potassium as an example, the reaction takes place in accordance with the following equation:

and sodium superoxide, NaO although the other alkali I metal superoxides, such as those of rubidium and cesium,

can also be used if desired.

Any quaternary ammonium superoxide (R N)O where R is an alkyl or aryl group, can also be used in our method to produce the corresponding quaternary ammonium ozonide. Thus, among the quaternary ammonium superoxides which may be used are tetraalkylammonium superoxides, such as tetraethylammonium superoxide, tetrapropylammonium superoxide, tetrabutylammonium superoxide and tetraheptylammonium superoxide; mixed tetraalkylammonium superoxides, such as cetyl-trimethylammonium superoxide; and arylalkylammonium superoxides, such as trimethylphenylammonium superoxide. Tetramethylammonium superoxide is quite stable, and tetramethylammonium ozonate is both stable and is exceedingly rich in oxygen because of its low molecular weight. Thus, in practicing our method with r 3,139,321 Patented June 30, 1964 the quaternary ammonium superoxides, we prefer at present to use tetramethylammonium superoxide.

The quaternary ammonium'superoxides are a relatively new class of compounds. They can be made by several methods, such as the metathetic reaction of the quaternary ammonium halide or hydroxide with potassium superoxide in liquid ammonia, or'by electrolysis of the quaternary ammonium halide in liquid ammonia, using, for example, a magnesium anode and a platinum cathode and a temperature between -65 C. and -80 0., followed by reaction of the electrolysis products with molecular oxygen. Such compounds and processes for their preparation are also disclosed in the copending, co-assigned applications of Hashman and Renforth Serial No. 92,090, filed February 27, 1961, which is a continuation-in-part of abandoned application, Serial No. 832,864, filed August 10, 1959, and Hashrnan and Berkstresser Serial No.

97,388, filed March 21, l961,which is a continuation-inpart of abandoned application Serial No. 832,863, filed August 1 0, 1959.

Alkaline earth metal ozonides are also made by our method from the corresponding alkaline earth metal superoxides. Thus, for example, calcium superoxide, CaO barium superoxide, BaO and strontium superoxide, SrO can each be used to produce the corresponding ozonide by the method described herein.

The temperature at which the reaction is carried out is not critical, but it should be considered inorder to obtain the best yields. Ordinary ambient temperatures, i.e., about 20 to 30 C., can be used, but because of the tendency of the ozonides to decompose ateven moderately elevated temperatures it is preferred to use low temperatures. Temperatures as low as 80" C. and lower are feasible for use in carrying out the process, but the reac tion at such low temperatures is quite slow." The pre-' ferred temperature'is about 0 C., where the reaction takes place at a. satisfactory ratejwhile little or no decomposition is ordinarily encountered. v ll-ligher temperatures than 30 C. should beavoided, except inthe' case desired.- In all cases, the course of the reaction is marked by a pronounced color change; that is, as'the ozonide is produced, the reaction mixture gradually becomes an intense red. If decomposition of the product is en-' countered, the color fades; thus with any particular reaction system the eifect of the reaction conditions can easily be observed and modified if necessary.

It is not necessary to use pure ozone in carrying out our process. Rather dilute concentrations of ozone and oxygen, i.e., about 5% as produced in ordinary ozonizers, are satisfactory and are generally used. However, when higher concentrations are used the reaction rate is increased and more product is obtained in a shorter time.

Both the superoxides and ozonide products are decomposed by water so that moisture should be excluded from the reaction site and from the product obtained. Thus, the ozone-oxygen mixture should be free from moisture, and storage containers should be blanketed with a dry gas.

In onedemonstration of the method of our invention, the process was carried out using 99% pure potassium superoxide, K02. The powdered potassium superoxide was placed on a porous plate within a closed reactor and the reactor was cooled to about 0 C. A dried gaseous mixture, 5% ozone in oxygen, was then passed through the superoxide for about three hours, the reactor was occasionally agitated in order to break up the superoxide and to expose fresh surfaces to the ozone. At the end of this time, the product mixture was extracted with liquid ammonia in order to separate the product from unreacted superoxide. After the liquid ammonia had been evaporated about 480 milligrams of a dark red solid were obtained. Chemical and X-ray diffraction anlyses were used to identify this productas potassium ozonide, K

In other such examples, other ozonides,'including, for example, sodium ozonide and tetramethylammonium ozonide, were prepared at various temperatures from 112 C. tov about 25 C. It was found that the best yields were obtained at about 0 C. or slightly above. Analysis and positive identificationof the products was made through X-ray' ditfraction analysis. It was further demonstrated that the process is'applicableto alkaline earth metal superoxides to produce alkaline earth metal ozonides, such as barium ozonide and calcium ozonide;

The ozonides which are made, by the method of our invention have several uses. They may be used as oxidizing agents, where they exhibit powerful properties such that organic compounds can be oxidized to carbon di 5. A method in accordance with claim 1 in which the alkali metal superoxide is potassium superoxide and the alkali metal ozonide produced is potassium ozonide.

6. A method of producing quaternary ammonium ozonide of the'tormula R NO Where R is alkyl, which comprises reacting ozone with a tetraalkylamrnonium superoxide and recovering the quaternary ammonium ozonide thus produced. I

7. A method in accordance with claim- 6 in which the reaction is carried out at a temperature about 0 C.

8; A method in accordance with claim 6 in which the ozone is admixed with oxygen. 7

9. A method in. accordance with claim 6 in which the tetraalkylamm onium superoxide is tetramethylam-nonium oxide, thereby providing an analytical method for determining the amount of carbon in such compounds. The ozonides can also-be used as a source of oxygen, as, for example, in self-contained breathing apparatus or in confined spaces such as may be encountered in submarines. Oxygen is released from these compounds upon contact with moisture so that by passing exhaled air containing moisture through a container of ozonides in suitable apparatus fresh oxygen is produced. The equipment used may be similar to well-knownapparatus used to produce breathing from superoxides.

According to the provisions of the patent statutes, we have explained the principle and modeof practicing our invention and havevdescribedwhat we now consider to. be its best embodiments. However, We desire to have it understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described. y

We claim:

1. A method of producing alkali metal ozonides, M0

superoxde and the tetraalkylammonium ozonide produced is tetramethylammdnium ozonide.

10. A method of producing alkaline earth metal ozonides, M0 where M is an alkaline earth metal, which com prises reacting ozone with alkaline earth metal superoxide'and recovering the alkaline earth metal ozonide thus produced. V

11'. A method in accordance with claim 10 -in which the reaction is carried out at a temperature about 0 C.

12. A method in accordancewith claim 10 in which the ozone is admixed with oxygen.

13'. A method in accordance with claim 10 in which the alkaline earth metal superoxide is barium superoxide and the alkaline earth metal ozonide produced is barium ozonide.

14. A method in accordance. with claim 10 in'which the alkaline earth metal superoxide is calcium superoxide and the alkaline earth metal ozonide produced is calcium ozonide.

where M is an alkali metal, which comprises reacting ozonewith an alkali metal superoxide and recovering the alkali metal ozonide'thus produced.

2. A method in accordance with claim 1 in which the reaction is carried out at a temperature of about 0 C.

3. A method in accordance with claim 1 in which the ozone is admixed with oxygen. 3

4. A' method'in accordance with claim 1 in which the alkali metal superoxide is sodium superoxide and" the alkali metal ozonide produced is sodium ozonide.

References Cited in the file of this patent UNITED STATES PATENTS Cunningham Mar. 5, 1957 OTHER REFERENCES 7 Strecker et 'al.: Chemische Berichte, vol. 53, part II, pp. 2096-2101, 2102, 2105-2107, 2110-2113 (1920). Mellor: Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. 1, page 908 (1922). V Doklady 'Akad. Nauk S.S.S.R., vol. 77, pp. 69-72 (1951).

Doklady Akad. Nauk S.S.S.R., vol. 118, No. 1, pp. '127 1958); found in Consolidated Translation Survey,

. 7 December 1958, No.. 12, January 21, 1959, page 71. 

1. A METHOD OF PRODUCING ALKALI METAL OZONIDES, MO2 WHERE M IS AN ALKALI METAL, WHICH COMPRISES REACTING OZONE WITH AN ALKALI METAL SUPEROXIDE AND RECOVERING THE ALKALI METAL OZONIDE THUS PRODUCED.
 6. A METHOD OF PRODUCING QUATERNARY ANOMIUM OZONIDE OF THE FORMULA R4NO3, WHERE R IS ALKYL, WHICH COMPRISES REACTING OZONE WITH A TERTRAAYLAMMONIUM SUPEROXIDE AND RECOVERING THE QUATERNARY AMMONIUM OZONIDE THUS PRODUCED. 